BR112019009192B1 - PEROXIDE CURABLE POLYOLFIN COMPOSITION, METHOD OF PREPARING A PEROXIDE CURABLE POLYOLFIN COMPOSITION, PEROXIDE CURABLE POLYOLFIN PRODUCT, ARTICLE OF MANUFACTURING, COATED CONDUCTOR AND METHOD OF CONDUCTING ELECTRICITY - Google Patents

Abstract

A peroxide curable polyolefin composition comprising a peroxide curable polyolefin prepolymer, an organic peroxide and 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2 ,6-bis(1,1-dimethylethyl)-phenol. Also, a peroxide-cured polyolefin product prepared therefrom, methods of making and using the same, and articles containing or made therefrom.

Description

FIELD OF THE INVENTION

[0001] The field of the invention includes a peroxide-curable polyolefin composition, a peroxide-curable polyolefin product prepared therefrom, methods of making and using the same, and articles containing or made therefrom.

INTRODUCTION

[0002] Various types of curable polymeric compositions are mentioned in US 6,187,847; US 6,656,986; US 8,808,968 B2; US 8,455,580 B2; US 9,403,933 B2; US 9,329,480 B2; US 2010/0276057; US 2012/0329353; WO 2014/096951; and WO 2014/204944.

SUMMARY

[0003] Compositions containing peroxides and sulfur-based antioxidants are known to suffer from instability problems. Amines are added to these compositions to lessen or prevent such instability. We have unexpectedly discovered peroxide-curable polyolefin compositions containing sulfur-based antioxidants, peroxides and amines that suffer from peroxide instability problems. These problematic compositions contain a peroxide curable polyolefin resin, an organic peroxide and: (a) a combination of antioxidants CYANOX 1790 (tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1 ,3,5-triazine-2,4,6-trione) and DSTDP (distearyl dithiodipropionate) and NAUGARD 445 (bis(4-(1-methyl-1-phenylethyl)phenyl)amine) or (b) a combination of the antioxidant LOWINOX TBP-6 (2,2'-thiobis(6-t-butyl-4-methylphenol) and the HALS (hindered amine light stabilizer) LOWILITE 62 (butanedioic acid dimethyl ether, polymer with 4-hydroxy -2,2,6,6-tetramethyl-1-piperidine-ethanol.) It would make scientific sense to look for new peroxide-curable polyolefin compositions that have the antioxidant properties of the problematic compositions, but avoid the combination of additives found in (a) or (b). One problem, therefore, would be to formulate a new peroxide-curable polyolefin that contains a peroxide-curable polyolefin resin, an organic peroxide and one or more antioxidants, and optionally a HALS, that contains combinations of functional groups found in (a) or (b) and has the robust stability of peroxide.

[0004] Our technical solution to this problem includes a new peroxide-curable polyolefin composition that has antioxidant properties and does not undergo peroxide instability. The peroxide curable polyolefin composition comprises a peroxide curable polyolefin resin, an organic peroxide and 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2, 6-bis(1,1-dimethylethyl)-phenol ("BOTAP"). Also provided are a peroxide-cured polyolefin product prepared therefrom, methods of making and using the same, and articles containing or made therefrom. The antioxidant BOTAP contains many of the same functional groups found divided between the components of (a) or (b), although in the same molecule. This fact makes the robust peroxide stability of the composition and product of the invention surprising. DETAILED DESCRIPTION

[0005] The Table of Contents and Abstract are incorporated herein by reference. Examples of inventive embodiments include the following numbered aspects.

[0006] Aspect 1. A peroxide-curable polyolefin composition comprising constituents (A) to (C): (A) a peroxide-curable polyolefin resin, (B) an organic peroxide, and (C) 4-[[ 4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-bis(1,1-dimethylethyl)-phenol ("BOTAP"); wherein the peroxide-curable polyolefin composition contains from 95.0 to 99.70 weight percent (weight %) of (A), from 0.20 to 2.5 weight percent of (B) and 0 .01 to 0.50% by weight of (C), all based on % by weight peroxide curable polyolefin composition total. When a sum of the % by weight of constituents (A) to (C) is less than 100.00% by weight, the peroxide curable polyolefin composition further contains at least one additional constituent, such as constituents (D) to ( K) described later.

[0007] Aspect 2. The peroxide curable polyolefin composition of Aspect 1 wherein the peroxide curable polyolefin resin (A) is (i) a peroxide curable polyethylene resin ("pcPE"); or (ii) a pcPE which is a peroxide curable low density polyethylene resin ("pcLDPE"); or (iii) a pcPE which is a peroxide curable high density polyethylene resin ("pcHDPE"); or (iii) a pcPE which is a peroxide curable high density polyethylene resin ("pcHDPE"); or (iv) a pcPE which is a blend of a copolymer of ethylene (C1-C4)alkyl acrylate (EAA) and a peroxide curable polyethylene ("pcPE"); or (v) a pcPE which is a pcLDPE characterized by a melt index (190° C., 2.16 kg), “I2”, of 0.5 to 3.0 grams per 10 minutes (g/10 min. , for example, 2.1 g/10 min.) and a density of 0.90 to 0.95 grams per cubic centimeter (g/cm3, for example, 0.92 g/cm3); or (vi) a combination of any two or more of (i) through (iv). In some aspects, the I 2 is from 1.0 to 2.9 g/10 min, alternatively from 1.5 to 2.6 g/10 min, alternatively from 2.0 to 2.5 g/10 min.

[0008] Aspect 3. The peroxide-curable polyolefin composition of Aspect 1 or 2 wherein the organic peroxide (B) is dicumyl peroxide.

[0009] Aspect 4. The peroxide-curable polyolefin composition of any one of Aspects 1 to 3 wherein (i) the organic peroxide (B) is from 0.20 to 2.10% by weight; or (ii) the (B) organic peroxide is from 0.30 to 2.00% by weight, alternatively from 0.50 to 2.00% by weight; or (iii) the (C) BOTAP is from 0.015 to 0.50% by weight; or (iv) the (C) BOTAP is from 0.05 to 0.42% by weight; or (v) or a combination of (i) and (iii), (i) and (iv), (ii) and (iii), or (ii) and (iv); wherein all % by weight based on the total weight of the peroxide curable polyolefin composition.

[0010] Aspect 5. The peroxide-curable polyolefin composition of any one of Aspects 1 to 4 further comprising (i) at least one coagent (D) (H2C=C(H)(CH2)b-functional), wherein the subscript b is an integer from 0 to 2; 1 to 4 or (ii) at least one (E) second antioxidant; or (iii) (F) a hindered amine light stabilizer ("HALS"); or (iv) (G) a flame retardant; or (v) (H) a water tree retardant or electrical tree retardant; or (vi) (I) a dye; or (vii) (J) a methyl radical scavenger; or (viii) (K) an aromatic liquid or saturated hydrocarbon (LASH); or (ix) a combination of (i) and (ii); or (x) a combination of (i), (ii) and at least one of (iii) through (viii); or (xi) a combination of (i), (ii), (iii) and optionally 0 to 2 of (iv) to (viii); all of which the combined weight of (D) to (K) is >0 to 4.69% by weight of the total weight of the peroxide curable polyolefin composition.

[0011] Aspect 6. The peroxide-curable polyolefin composition of Aspect 5 wherein: (i) the at least one coagent (D) (H2C=C(H)(CH2)b-functional) is alpha-methylstyrene dimer ("AMSD") or a multi-(H2C=C(H)(CH2)b-functional) coagent that has two or three groups (H2C=C(H)(CH2)b-, where the subscript b is as defined before or after, or (ii) the at least one second antioxidant (E) is absent, tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine -2,4,6-trione or 4,4'-thiobis(2-t-butyl-5-methylphenol; or (iii) (F)HALS is butanedioic acid dimethyl ester, polymer with 4-hydroxy-2, 2,6,6-tetramethyl-1-piperidine-ethanol or (iv) the flame retardant (G) is a metal hydroxide, a swelling compound or a halogenated compound, or (v) the tree retardant in water (H ) or electrical tree retardant which is a silane or a polyethylene glycol ("PEG") or (vi) the dye (I) is carbon black, or (vii) the methyl radical scavenger (J) is a derivative of 2, 2,6,6-tetramethyl-1-piperidinyl-N-oxyl (derived from "TEMPO"); or (viii) the (K)LASH is an arene substituted by an alkane or alkyl; or (ix) a combination of (i) and (ii); or (x) a combination of (i), (ii) and at least one of (iii) through (viii); or (xi) a combination of (i), (ii), (iii) and optionally 0 to 2 of (iv) to (viii); and wherein each of constituents (D), (F), (G), (H), (I), (J) and (K) is independently (a) from 0.30 to 2.10% by weight ; or (b) from 0.05 to 0.5% by weight; or (c) from 0.010 to 0.35% by weight; and wherein each second antioxidant (E) independently is (a) from 0.01 to 0.2% by weight; or (b) from 0.01 to 0.10% by weight; wherein the entire weight % based on the total weight of the peroxide curable polyolefin composition and the combined weight of (D) through (K) is > 0.01 to 4.69% by weight of the total weight of the peroxide composition peroxide curable polyolefin.

[0012] Aspect 7. A method of preparing a peroxide-curable polyolefin composition, the method comprising contacting effective amounts of constituents (A) to (C) with: (A) a peroxide-curable polyolefin resin, (B) ) an organic peroxide, and (C) 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-bis(1,1-dimethylethyl)- phenol ("BOTAP"); to give the peroxide-curable composition, wherein the peroxide-curable polyolefin composition contains from 95.0 to 99.70 weight percent (wt%) of (A), from 0.20 to 2.5% by weight of (B) and from 0.01 to 0.50% by weight of (C), all based on % by weight peroxide curable polyolefin composition total. When the sum of % by weight of constituents (A) to (C) is less than 100.00% by weight, the peroxide curable polyolefin composition further contains at least one additional constituent, such as constituents (D) to ( K) described above.

[0013] Aspect 8. A peroxide cured polyolefin product which is a reaction product of curing the peroxide curable polyolefin composition of any one of Aspects 1 to 6 to give the peroxide cured polyolefin product. The peroxide-cured polyolefin product differs in structure from its peroxide-curable polyolefin composition from which it is made (e.g., crosslink density or extent of cure, as measured by mobile matrix rheometer (MDR), content of gel or thermal carry-over/thermal adjustment measurements).

[0014] Aspect 9. An article of manufacture comprising a molded form of the peroxide-cured polyolefin product of aspect 8.

[0015] Aspect 10. A coated conductor comprising a conductive core and an insulating layer at least partially covering the conductive core, wherein at least a portion of the insulating layer comprises the peroxide-curable polyolefin composition of any one of the aspects 1 to 6 or the peroxide-cured polyolefin product of aspect 8. The coated conductor can be a useful electrical cable for transmitting electricity.

[0016] Aspect 11. A method of conducting electricity, the method comprising applying a voltage across the conductive core of the coated conductor of aspect 10 so as to generate a flow of electricity through the conductive core.

[0017] Peroxide curable polyolefin composition. The total weight of all constituents is 100% by weight. The peroxide curable polymeric composition contains constituents (A) to (C), described in more detail later. The peroxide curable polyolefin composition contains (A) peroxide curable polyolefin resin, which are crosslinkable macromolecules that are substantially free or free of heteroatoms (eg, halogen, N, O, S, P). Under curing conditions (typically comprising heating to a temperature above 160 °C), organic peroxide (B) forms oxygen radicals. The O-radicals extract hydrogen atoms from the inner carbon atoms in the main chains or side chains of the peroxide-curable polyolefin resin (A), thus generating free radicals from the inner polyolefin chain on carbon atoms. The carbon radicals couple to form the peroxide cured polyolefin product.

[0018] The peroxide-curable polyolefin composition may be a one-part formulation, alternatively a two-part formulation. The two-part formulation may comprise first and second parts, the first part consisting essentially of (A) peroxide-curable polyolefin resin; wherein the second part consists essentially of an additive masterbatch composition comprising (B) organic peroxide and any optional constituents (e.g. (D) to (K)); wherein the constituent (C) can be in the first or second part or in both. There is no inherent reason why any combination of constituents (B) and (C); and constituents (D) to (K), if any, cannot be in the one-part formulation or in the first part or second part of the two-part formulation. There are generally no incompatibilities between constituents (A) to (K) because the inventive embodiments solve a problem of acid-catalyzed decomposition of organic peroxide (B).

[0019] Constituent (A): Peroxide curable polyolefin resin. The peroxide-curable polyolefin resin comprises polyolefin macromolecules capable of becoming crosslinkable (crosslinkable macromolecules) through a curing reaction under curing conditions, thereby forming a network polymer, which is also referred to herein as the peroxide-cured polyolefin product. peroxide. Crosslinkable polyolefin macromolecules contain, on average, per molecule, more than two hydrogen atoms extracted from carbon (CH). The crosslinkable polyolefin macromolecules can be homopolymers or copolymers. The copolymer can be a dipolymer prepared from ethylene and a comonomer. The copolymer can be a terpolymer prepared from ethylene and two different comonomers. For homopolymers, the monomer can be ethylene or an alpha-olefin (C3-C20). For copolymers, the monomer can be ethylene, alternatively propylene; and the comonomer(s) may be an alpha-olefin (C3-C20). Typically, the alpha-olefin (C3-C20) is an alpha-olefin (C3-C10). Typically, alpha-olefin (C3-C10) is propene, 1-butene, 1-hexene or 1-octene; alternatively propylene, 1-butene or 1-hexene; alternatively propylene; alternatively 1-butene; alternatively 1-hexene. Examples of suitable (A) are described above and below. (A) may be in a divided solid form. The divided solid form can comprise granules, pellets, powder or a combination of any two or more thereof.

[0020] In some aspects, the peroxide curable polyolefin (A) resin is an ethylene-based polymer. As used herein, "ethylene-based" polymers are macromolecules prepared from monomers of ethylene as the primary monomer component (i.e., greater than 50 percent by weight ("% by weight")), although other comonomers can also be employed. Thus, the ethylene-based polymer includes polyethylene homopolymers and copolymers. The ethylene-based copolymer may be an ethylene/alpha-olefin interpolymer ("α-olefin") with an α-olefin content of at least 1% by weight, at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight or at least 25% by weight based on the total weight of the interpolymer. Such interpolymers can have an α-olefin content of less than 50% by weight, less than 45% by weight, less than 40% by weight, or less than 35% by weight based on the total interpolymer weight. When an α-olefin is employed, the α-olefin may be a linear, branched or cyclic (C3C20) α-olefin (ie, having 3 to 20 carbon atoms). Examples of α-olefins (C1-C20) include propene, 1-butene, 4-methyl-1-pentene, 1-hexane, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1 -octadecene. α-olefins can also have a cyclic structure, such as cyclohexane or cyclopentane, resulting in an α-olefin, such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane. Exemplary ethylene/α-olefin interpolymers include ethylene/propylene, ethylene/1-butene, ethylene/1-hexane, ethylene/1-octene, ethylene/propylene/1-octene, ethylene/propylene/1-butene and ethylene/1 -butene/1-octene. Examples of suitable ethylene-based polymers are the polyethylenes described in US 6,656,986 B2, such as column 2, line 62, column 5, line 6. For example, the high pressure reactor processes used to prepare so-called pcLDPE of the high-pressure reactor are described beginning in column 3, row 21.

[0021] The ethylene-based polymer of aspects of constituent (A) can be used alone or in combination with one or more other types of ethylene-based polymers (for example, a mixture of two or more ethylene-based polymers , which differ from each other by composition and monomer content, catalytic method of preparation, etc.). If an ethylene-based polymer blend is used, the polymers can be blended by any process in the reactor or post-reactor. In some embodiments, the ethylene-based polymer is a low density polyethylene ("LDPE"), a linear low density polyethylene ("LLDPE"), a very low density polyethylene ("VLDPE"), or a combination or blend of two or more of them.

[0022] In some aspects of constituent (A), LDPEs are generally highly branched ethylene homopolymers and can be prepared through high pressure processes (ie HP-LDPE). LDPEs suitable for use in the present invention can have a density ranging from 0.91 to 0.94 g/cm3. In some embodiments, the ethylene-based polymer is a high pressure LDPE with a density of at least 0.915 g/cm3 but less than 0.94 g/cm3 or less than 0.93 g/cm3. Polymer densities provided herein are determined according to ASTM International ("ASTM") Method D792. LDPEs suitable for use herein may have a melt index (I2) of less than 40 g/10 min or range from 0.1 to 40 g/10 min or from 0.5 to 20 g/10 min or from 0.5 to 10 min. 5 g/10 min or 1 to 3 g/10 min or an I2 of 2 g/10 min. Melt indices given herein are determined in accordance with ASTM method D1238. Unless otherwise noted, melt indices are determined at 190 °C and 2.16 kg (ie, I2). Generally, LDPEs have a broad molecular weight distribution ("MWD"), resulting in a relatively high polydispersity index ("PDI"; the ratio of weight average molecular weight to number average molecular weight).

[0023] In some aspects of constituent (A), the ethylene-based polymer may be an LLDPE. LLDPEs are generally ethylene-based polymers having a heterogeneous comonomer distribution (eg, α-olefin monomer) and are characterized by short-chain branching. For example, the LLDPEs can be copolymers of ethylene and α-olefin monomers, such as those described above. LLDPEs suitable for use in the present invention can have a density ranging from 0.916 to 0.925 g/cm 3 . LLDPEs suitable for use in the present invention may have a melt index (I 2 ) ranging from 0.1 to 40 g/10 min or from 1 to 20 g/10 min or from 3 to 8 g/10 min.

[0024] In some aspects of constituent (A), the ethylene-based polymer may contain one or more polar comonomers, such as vinyl acrylates or acetates. Additionally, mixtures of non-polar ethylene-based polymers such as those described above and polar copolymers (for example, those copolymers containing one or more types of polar comonomers) can also be used. In addition, polyolefin elastomers, such as those commercially available under the tradename ENGAGE™ from The Dow Chemical Company, can be used as an ethylene-based polymer or in combination with one or more of the ethylene-based polymers described above. Polyolefin elastomers suitable for use in the present invention can have a density ranging between 0.857 g/cm3 and 0.908 g/cm3. Polyolefin elastomers suitable for use in the present invention may have a melt index (I 2 ) in the range of 0.1 to 30 g/10 min or 0.5 to 5 g/10 min.

[0025] Peroxide curable polyolefin resin (A) can be obtained from commercial suppliers or can be prepared by polymerizing a monomer to give homopolymer or copolymerizing a monomer and at least one and typically not more than three comonomers to give the copolymers . Suitable polymerization methods for making (A) are generally well known. They normally employ an olefin polymerization catalyst, such as the known Ziegler-Natta catalysts and/or the well known molecular catalysts. Such catalysts are well known. The catalysts are prepared by contacting the corresponding procatalysts with an activator such as an alkylaluminoxane (e.g. methylaluminoxane), a trialkylaluminum (e.g. triethylaluminium) and/or an organoborate compound (e.g. N,N-dimethylanilinium tetrakis). (pentafluorophenyl)borate) or organoborane compound (e.g. tris(pentafluorophenyl)borane). Ziegler-Natta procatalysts can be a titanium tetrachloride supported on magnesium chloride. Molecular pro-catalyst for olefin polymerizations may not be supported or supported. The molecular procatalyst is usually a metal complex with a well-defined structure. The molecular pro-catalyst can, upon activation, give a homogeneous single-site or multi-site (2 or 3 sites) molecular catalyst that is effective for polymerizing ethylene and alpha-olefins. The molecular procatalyst can be any molecular ligand-transition metal complex in which the transition metal is an element in Group 3 to 11 of the Periodic Table of Elements, including the lanthanides and actinides. In some aspects, the transition metal is Ti, Zr, Hf, V or Cr. In some aspects, the transition metal is selected from the group of any four of Ti, Zr, Hf, V and Cr. In some aspects, the transition metal is Fe, Co, Ni or Pd. In some aspects, the molecular catalyst can polymerize the olefins in the gas phase or in solution under high temperature solution process conditions. In some aspects, the molecular catalyst may be selected from any one or more of bis-phenylphenoxy catalysts, restricted geometry catalysts, iminostarch type catalysts, pyridylamide catalysts, iminoenamido catalysts, aminotroponimine catalysts, quinoline amido catalysts, bis( phenoxyimine) catalysts, phosphinamide catalysts and metallocene catalysts. Suitable polymerization methods for making (A) are well known and include gas phase, solution phase and slurry phase methods. The gas phase process may be a gas phase ethylene polymerization process, such as the UNIPOL™ PE process.

[0026] The production processes used for preparing ethylene-based polymers are wide and varied and known in the art. Any conventional or futurely discovered production process for producing ethylene-based polymers having the properties described above can be employed for preparing the ethylene-based polymers described herein. In general, the polymerization can be carried out under conditions known in the art for polymerization reactions of the Ziegler-Natta, chromium oxide or Kaminsky-Sinn type, i.e. at temperatures of 0 to 250 °C or 30 or 200 °C and pressures from atmospheric to 10,000 atmospheres (approximately 1,013 MegaPascal ("MPa")). In most polymerization reactions, the molar ratio of catalyst to polymerizable compounds used is from 10-12:1 to 10-1:1 or from 10-9:1 to 10-5:1.

[0027] Constituent (B): organic peroxide. The organic peroxide (B) can be of the formula RO-O-O-RO, where each RO is independently an alkyl group (C1-C20) or an aryl group (C6-C20). Each alkyl group (C1-C20) is independently unsubstituted or substituted with 1 or 2 aryl groups (C6C12). Each aryl group (C6-C20) is unsubstituted or substituted with 1 to 4 alkyl groups (C1-C10). The organic peroxide (B) can be any of the organic peroxides described above. Alternatively, (B) may be bis(1,1-dimethylethyl) peroxide; bis(1,1-dimethylpropyl) peroxide; 2,5-dimethyl-2,5-bis(1,1-dimethylethylperoxy)hexane; 2,5-dimethyl-2,5-bis(1,1-dimethylethylperoxy)hexyne; 4,4-bis(1,1-dimethylethylperoxy) valeric acid, butyl ester; 1,1-bis(1,1-dimethylethylperoxy)-3,3,5-trimethylcyclohexane; or benzoyl peroxide. Alternatively (B) may be tert-butyl peroxybenzoate, di-tert-amyl peroxide ("DTAP"), bis(alpha-t-butyl-peroxy-isopropyl) benzene ("BIPB"), isopropylcumyl-t- butyl, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-bis(t-butylperoxy)-2,5-dimethylhexane, 2,5-bis(t-butylperoxy)-2,5- dimethylhexine-3,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, isopropylcumyl cumyl peroxide, 4,4-di(tert-butylperoxy)butyl valerate, di( isopropylcumyl) and combinations of two or more of these. In some aspects, only a single type of organic peroxide (B) is used, for example dicumyl peroxide.

O BOTAP está comercialmente disponível como BNX® 565 da Mayzo, Inc., Suwanee, Georgia, USA; e como IRGANOX™ 565 da BASF Corporation, Florham Park, Nova Jersey, EUA. Alternativamente, o BOTAP pode ser sintetizado seguindo métodos conhecidos da literatura de sintetizar o BOTAP.[0028] Constituent (C): 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-bis(1,1-dimethylethyl)- phenol, known as 4-[[4,6-bis(octylsulfanyl)-1,3,5-triazin-2-yl]amino]-2,6-di(tertiary-butyl)-phenol and abbreviated as “BOTAP” . BOTAP has CAS number 991-84-4 and the following chemical structure:

BOTAP is commercially available as BNX® 565 from Mayzo, Inc., Suwanee, Georgia, USA; and as IRGANOX™ 565 from BASF Corporation, Florham Park, New Jersey, USA. Alternatively, BOTAP can be synthesized following known literature methods of synthesizing BOTAP.

[0029] Optionally, the peroxide-curable polyolefin composition and/or the peroxide-curable polyolefin product made therefrom, may contain zero, one or more coagents and/or zero, one or more additives and/or zero, one or more more liquid aromatic or saturated hydrocarbons (LASH). In addition to constituents (D) to (K) described above and detailed below, the peroxide-curable polyolefin composition may further comprise 0.005 to 0.5% by weight of each one or more additives selected from a carrier resin, corrosion inhibitors, (e.g. SnSO4), fillers, lubricants, processing aids, antiblocking agents, antistatic agents, nucleating agents, abrasion retardants, slip agents, plasticizers, tackifiers, surfactants, extender oils, acid removing agents, voltage stabilizers and metal deactivators. The carrier resin may be used to prepare an additive masterbatch to facilitate mixing or blending of the additives and/or (C), and in some aspects (B), with the peroxide curable polyolefin resin (A) as described further below. . The filler can be a hydrophobized fumed silica, such as those commercially available under the trade name CAB-O-SIL from Cabot Corporation. The processing aid may be an organic processing aid such as a fluoropolymer or a silicone processing aid such as a polyorganosiloxane or a fluorine-functionalized polyorganosiloxane and may function to improve melt flow of the heat-curable polyolefin composition. peroxide through a machine such as an extruder. The inclusion of co-agent(s) and/or additive(s) and/or LASH(s) in, or exclusion thereof from, the composition and/or product is optional.

[0030] Coagents, such as at least one coagent (D) (H2C=C(H)(CH2)b-functional), can be used in the peroxide-curable polyolefin composition to increase the density of crosslinks in the polyolefin product cured by peroxide. Additives, such as constituents (E) to (J), may be used to impart to either the composition and/or the product one or more beneficial properties other than crosslinking density. The (K)LASH(s) can be used to prepare, purge or transport the peroxide curable polymer composition or the peroxide cured polyolefin product. Coagents and additives are compounds/materials distinct from constituents (A) to (C) and from each other and from LASH. Additives are normally not removed from the peroxide cured polyolefin product. Coagents typically react to form crosslinks in the peroxide cured polyolefin product. LASH is chemically inert and may be volatile.

[0031] The optional constituent (D): the functional coagent H2C=C(H)(CH2)b. Also called crosslinker (H2C=C(H)(CH2)b-functional). The H2C=C(H)(CH2)b functional coagent can have 1 or more, typically at most 6, (C=C(H)(CH2)b functional groups on average per molecule. The subscript b is an integer from 0 , 1 or 2; alternatively 0 or 1; alternatively 1 or 2; alternatively 0 or 3; alternatively 0; alternatively 1; alternatively 2. Examples of functional groups (H2C=C(H)(CH2)b are vinyl groups (b is 0), allyl groups (b is 1) and butenyl groups (b is 2). The (D) can have a molecular weight molecule from 110 to 600 grams/mol (g/mol), alternatively from 200 to 550 g/mol. mol Examples of (D) with 1 functional group (H2C=C(H)(CH2)b include alpha-methylstyrene dimer ("AMSD"; CAS No. 6362-80-7). multi(H2C=C(H)(CH2)b) functional coagent having 2, 3, or 4 groups (H2C=C(H)(CH2)b. Examples of the multi(H2C=C(H)(CH2)b) functional coagent ) include triallyl isocyanurate (“TAIC”); triallyl cyanurate (“TAC”); triallyl trimellitate (“TATM”; CAS No. 2694-54-4); N,N,N',N',N' ,N'-hexa-allyl-1,3,5-triazine-2,4,6-triamine ("HATATA"; also known as N2,N2,N4,N4,N6,N6-hexa-allyl-1,3,5-triazine-2,4,6-triamine); triallyl orthoformate; pentaerythritol triallyl ether; triallyl citrate; and triallyl aconitate; acrylate-based coagents; multivinyl coagents; and other coagents, such as those described in US 5,346,961 and 4,018,852. Examples of suitable acrylate-based coagents are trimethylolpropane triacrylate ("TMPTA"); trimethyl trimethylolpropane acrylate ("TMPTMA"); ethoxylated bisphenol A dimethacrylate; 1,6-hexanediol diacrylate; pentaerythritol tetraacrylate; dipentaerythritol pentaacrylate; tris(2-hydroxyethyl)isocyanurate triacrylate; and propoxylated glyceryl triacrylate. Examples of suitable multi-vinyl co-agents are polybutadiene with a high 1,2-divinyl content; and trivinyl cyclohexane ("TVCH"). In some respects (D) is AMSD, TAC, TAIC, HATATA or TMPTA; alternatively AMSD, TAC or TAIC; alternatively AMSD. (D) functions to increase the crosslink density in the resulting cured polyolefin product relative to the crosslink density that can be obtained in the absence of (D).

[0032] The optional constituent (E) second antioxidant. (E) functions to provide additive or synergistic antioxidant properties to the peroxide curable polyolefin composition and/or peroxide cured polyolefin product without impeding the decrease in peroxide instability. Examples of suitable (E) are described above. (E) may be bis(4-(1-methyl-1-phenylethyl)phenyl)amine (eg NAUGARD 445). Alternatively, (E) may be 2,2'-thiobis(2-t-butyl-5-methylphenol (CAS No. 90-66-4, commercially LOWINOX TBM-6); 2,2'-thiobis(6-t -butyl-4-methylphenol (CAS No. 90-66-4, commercially LOWINOX TBP-6); tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5 -triazine-2,4,6-trione (e.g. CYANOX 1790) or pentaerythritol tetrakis(3-(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)propionate (e.g. IRGANOX 1010, No. CAS 6683-19-8) 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid 2,2'-thiodiethanediyl ester (eg, IRGANOX 1035, CAS number 41484-35-9), or distearyl thiodipropionate ("DSTDP"). In some aspects (E) is absent. In some aspects, (E) is present and is 2,2'-thiobis(2-t-butyl-5-methylphenol) (eg, LOWINOX TBM-6 ) or tris [(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4,6-trione (e.g. CYANOX 1790) or alternatively tris [(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4,6-trione (e.g. CYANOX 1790).

[0033] The optional constituent (F) hindered amine light stabilizer (HALS). (F) is a compound that inhibits oxidative degradation and can also reduce acid-catalyzed degradation, if any, of the organic peroxide (B). Examples of suitable (F) are butanedioic acid dimethyl ester, polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine-ethanol (CAS No. 65447-77-0, commercially LOWILITE 62).

[0034] The optional component (G) flame retardant. The (G) functions to decrease the flammability of the peroxide cured polyolefin product. Examples of suitable (G) are described above or below.

[0035] The optional component (H) water tree retardant or electrical tree retardant. Water tree growth retardant is a compound that inhibits water tree growth, which is a process by which polyolefins degrade when exposed to the combined effects of an electric field and moisture or humidity. Electrical arborescence retardant is a compound that inhibits electrical arborescence, which is an electrical pre-breakdown process in solid electrical insulation due to partial electrical discharges. Electric arborescence can occur in the absence of water. Water arborescence or electrical arborescence are problems for electrical cables that contain a coated conductor in which the coating contains a polyolefin. Examples of suitable (H) are described above or below.

[0036] The optional constituent (I) dye. For example, a pigment or dye. For example, carbon black or titanium dioxide.

[0037] The optional constituent (J) of the methyl radical (J). The (J) reacts with methyl radicals in the composition or product. (J) may be a "TEMPO" derivative of 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl. Examples include 4-acryloxy-2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (CAS No. 21270-85-9, "TEMPO acrylate"), 4-allyloxy-2,2,6,6 -tetramethyl-1-piperidinyl-N-oxyl (CAS No. 217496-13-4, "allyl TEMPO"); bis(2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl) sebacate (CAS No. 251692-9, "bis TEMPO")); N,N-bis(acryloyl-4-amino)-2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (CAS No. 1692896-32-4, "TEMPO diacrylamide"); and N-acryloyl-4-amino-2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (CAS No. 21270-88-2, "TEMPO monoacrylamide").

[0038] The optional constituent (K) aromatic or liquid saturated hydrocarbon (LASH). LASH may have a boiling point (101 kilopascals (kPa)) from 30° to 300°C, alternatively between 40° to 250°C, alternatively between 50° and 200°C. Examples of suitable LASH are 2-methylbutane, pentane, hexane, heptane, toluene, xylene(s) and combinations of any two or more thereof.

[0039] Aspects of the peroxide curable polyolefin composition may be referred to as unfilled composition when the filler is absent. Aspects of unfilled composition can be done by any suitable means. For example, an unfilled composition that contains constituent (A), with or without constituent (C), and with any optional constituents (D) through (K), but contains no filler or organic peroxide (B) and may or may not contain (C), can be done in a Brabender batch mixer, mixing the constituents for 3 minutes at 180 °C, melting temperature using cam blades at 30 revolutions per minute (rpm) to give an unfilled molten mixture, then allowing molten mixture to cool and then contacting the resulting cooled mixture by organic peroxide (B), and if (C) is not previously included, to provide the unfilled composition embodiments.

[0040] Aspects of the peroxide curable polyolefin composition may be referred to as a filled composition when it further includes a filler. Aspects of the completed composition can be done by any suitable means. For example, the filled composition aspects can be made in a Brabender batch mixer using a melting temperature of 180°C by first adding constituents (A) and with or without (C) to the mixer. Once constituents (A) and optionally (C) have begun to melt, add a charge, constituent (C) (if not already added) and optionally zero, one or more (E) second antioxidants, followed by any other additives (D) and (F) to (K) in the flow to give a molten filled mixture. Then, homogenize the filled molten mixture for about 3 minutes and allow the loaded molten mixture to cool and then bring the resulting cooled mixture into contact with organic peroxide (B) to give the appearance of the filled composition.

[0041] To facilitate mixing the peroxide-curable polyolefin resin of constituent (A) with constituent (C) and any optional constituents (D) to (K), and any of the other optional additives mentioned above not identified by the letter , the (C) and any additives may be supplied in the form of an additive masterbatch. The additive masterbatch can contain a dispersion of (C) and optionally one or more such additives (e.g., carbon black) in the carrier resin. The carrier resin may be a poly(1-butene-co-ethylene) copolymer. In the additive master mix, the carrier resin can be >90% by weight to <100% by weight and the (C) and any one or more optional additives together can be from >0% by weight to <10% by weight by weight total additive master mix. In some aspects, from 1 to 20 parts by weight of the additive masterbatch may be mixed or blended with 99 to 80 parts by weight of the peroxide curable polyolefin (A) resin to give a preparative blend of the mixture thereof, which can then be granulated according to the methods described here for giving granulates. The granulates can then be contacted with a suitable amount of the organic peroxide (B) to give the peroxide curable polyolefin composition. Alternatively, (D), if any, can be omitted from the additive master mix and instead soaked into the granules before, during or after soaking the granules with (B). Alternatively, the organic peroxide (B) can be included in the additive masterbatch and the temperature of the additive masterbatch during its preparation and mixing with (A) can be maintained well below the 10 hour half-life temperature of (B ).

[0042] The peroxide cured polyolefin product. The peroxide cured polyolefin product contains networked polyolefin resins that contain C-C bonding crosslinks. The networked polyolefin resins comprise peroxide-curable polyolefin (A) resin coupling products. The peroxide cured polyolefin product may also contain curing by-products, such as alcohol products, from the organic peroxide reaction (B). The peroxide cured polyolefin product may also contain the (C)BOTAP. When, optionally, the peroxide-curable polyolefin composition further contains one or more coagents, additives and/or optional LASH, the resulting peroxide-cured polyolefin product may also further contain the crosslinks formed from the coagents, additives and/or LASHs. LASHs can be removed from the peroxide-cured polyolefin product to give a peroxide-cured polyolefin product that is free of, or contains from >0 to <1% by weight of LASH. Such removal can be carried out by any suitable means, such as decantation, devolatilization, distillation, evaporation, filtration, inert gas spray (eg anhydrous N2 gas) and stripping. The peroxide cured polyolefin product may be in a divided solid form or in continuous form. The divided solid form can comprise granules, pellets, powder or a combination of any two or more thereof. The continuous form may be a molded part (eg blow molded part).

[0043] Test samples of unfilled and filled composition embodiments can be separately formed into compression molded plates. The mechanical properties of these compositions can be characterized using test samples cut from the compression molded boards.

[0044] Any compound included herein includes all isotopic forms thereof, including naturally abundant forms and/or isotopically enriched forms. The isotopically enriched forms may have additional uses, such as medical or anti-counterfeiting applications, where detection of the isotopically enriched form is useful in treatment or research.

[0045] The following applies unless otherwise noted. Alternatively, it precedes a distinct modality. ASTM means the standards organization, ASTM International, West Conshohocken, Pennsylvania, USA. IEC stands for the standards organization, International Electrotechnical Commission, Geneva, Switzerland. Any comparative example is used for illustration purposes only and should not be prior art. Exempt from or without means a complete absence of; alternatively undetectable. IUPAC is the International Union of Pure and Applied Chemistry (IUPAC Secretariat, Research Triangle Park, North Carolina, USA). May confer a permitted choice, not an imperative. Operative means functionally capable or effective. Optional means are(ally) absent (or excluded), alternatively, are present (or included). PPM are based on weight. Properties are measured using a standard test method and measurement conditions (eg viscosity: 23°C and 101.3 kPa). Ranges include endpoints, subranges, and integer and/or fractional values included, except that an integer range does not include fractional values. Ambient temperature: 23°C. ± 1°C. Substituted when referring to a compound means having, in place of hydrogen, one or more substituents, up to and including by substitution.

[0046] Advantageously we found that the antioxidant BOTAP contains many of the same functional groups found divided between tris [(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2, 4, 6-trione and DSTDP and optionally NAUGARD 445, although in the same molecule and yet the peroxide curable polyolefin composition of the invention has robust peroxide stability relative to a comparative composition utilizing (a) a combination of antioxidants CYANOX 1790 and DSTDP and NAUGARD 445 or (b) a combination of the antioxidant LOWINOX TBP-6 and the HALS LOWILITE 62; or (c) a combination of CYANOX 1790 and DSTDP antioxidants. An additional benefit is that the embodiments of these compositions/products also have a superior dissipation factor compared to combination (a), (b) or (c), even when similar functional groups of the invention are at the same concentration as combination (a) , (b) or (c). An added advantage is that BOTAP has less sweat than antioxidants such as CYANOX 1790 and NAUGARD 445.

[0047] Embodiments of the composition and product of the invention that additionally comprise at least one functional co-agent (H2C=C(H)(CH2)b) (D) and/or at least one second antioxidant (E) may have additional advantages, as well as better abrasion resistance. These characteristics make the inventive composition and product useful in a variety of applications, including as a component of a coating on a coated conductor, such as a coated wire or coated cable for use in the electrical or telecommunications industry, including medium voltage or high voltage. high voltage and extra-high voltage electrical cables.

[0048] Unless otherwise noted here, use the following preparations for characterizations.

[0049] Composition Preparation Methods. Melt blend constituents of peroxide curable polyolefin composition (from comparative or inventive examples) in a Banbury manufacturer using a typical composition temperature of 150°C, rotor speed of 60 to 65 revolutions per minute (rpm) or at a ZKS twin screw extruder using an extrusion temperature of 160 °C or higher (eg 200 °C) and a screw speed of 200 rpm. For laboratory scale procedures, use batch mixers and single screw extruders to mix and granulate. Soak the peroxide in the granules containing the mixed additives at 60° to 80°C for 6 to 24 hours.

[0050] Granulate Preparation Method. Mix the (A)pcPE and an appropriate amount of (C)BOTAP, plus any optional additives (e.g., any optional antioxidants), generally not including the multi functional coagent (H2C= C(H)(CH2)b, but not including organic peroxide (B), in a Brabender bowl at 200 °C for 3 minutes after flow to give a melt mix without multi functional coagent (H2C= C(H)(CH2)b, without organic peroxide. the melt mixture on a compression molding press and cut the flattened product into small strips. Pass the strips through a single screw extruder with a double mixing head at 180°C to form strands which are cut into small uniform granules, that are free of organic peroxide (B) and preferably free of multi functional coagent (H2C= C(H)(CH2)b) (D) Place the granules in a glass jar, place the glass jar in a preheated oven. -heated to 70 °C and heat the granules for 4 hours to give heated granules. Remove the glass jar containing the heated granules from the oven and spray an appropriate amount of: method (a): organic peroxide (B) or method ( b): Appropriate amounts of a combination of organic peroxide and multi(H2C=C(H)(CH2)b) coagent (B) on the heated granules to give powdered granules in the vial. The appropriate amount(s) is(are) calculated based on the weight of the molten mixture and the weight of the organic peroxide (B) and any multi(H2C=C(H)(CH2) functional coagent )b), not counting the weight(s) of volatile solvent(s) used to facilitate spraying. Suitable amounts are designed to give claimed concentrations according to the weight % ranges described above for organic peroxide (B) (e.g. 1.75% by weight or 1.8% by weight), (C) BOTAP (e.g. 0.12% by weight, 0.24% by weight, 0.36% by weight, or 0.42% by weight) and any multi(H2C=C(H)(CH2)b) functional coagent ( for example 0% by weight, 0.20% by weight or 0.35% by weight). Seal the jar and roll the granules for 10 minutes. Put the jar back in the oven at 70°C overnight to give the granules soak. Soaked granules prepared by method (a) were soaked by organic peroxide (B) (e.g. dicumyl peroxide) and soaked granules prepared by method (b) were soaked with an organic peroxide combination (b) (e.g. dicumyl peroxide) and multi(H2C=C(H)(CH2)b-functional) coagent (e.g. AMSD). Test soaked granules for dissipation factor, extent of cure and burn enhancement as described here.

[0051] Unless otherwise noted here, use the following test methods for characterizations. Soaked pellets prepared by method (a) or (b) of the Granule Preparation Method may be used unless otherwise indicated.

[0052] Density is measured in accordance with ASTM D792-13, Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (for testing solid plastics in liquids other than water, for example, in liquid 2-propanol). Record results in units of grams per cubic centimeter (g/cm3).

[0053] Dissipation Factor and Dielectric Constant Test Methods. The dissipation factor and dielectric constant are measured at an electrical voltage of 60 Hertz (Hz, voltage), 2 kilovolts per millimeter (kV/mm) and a temperature of 120 °C using an orientation at 2 kilovolts per millimeter (kV/mm ) per ASTM D150-11, Standard Test Methods for AC Loss and Permittivity (Dielectric Constant) Characteristics of Solid Electrical Insulation, on a 1 millimeter plate using compression molded cured samples of prepared peroxide cured polyolefin product from soaked granules of the peroxide curable polyolefin composition prepared according to the Granule Preparation Method. The lower the dissipation factor, the better the peroxide-curable compositions/peroxide-cured polyolefin product are for use as electrical insulating layers in coated conductor coatings, and therefore the better these compositions/products are for use as electrical insulators in electrical or telecommunications cables and applications. In some aspects, the peroxide curable polyolefin composition and the peroxide cured polyolefin product prepared therefrom are characterized by a dissipation factor measured in accordance with the Dissipation Factor Test Method of 0.028% to 0.099%.

[0054] The melt index, I2, for polyethylene is measured according to ASTM D1238-04, Standard Test Method for Flow Rates of Thermoplastics by Extrusion Plate, using conditions of 190 °C / 2.16 kg (kg ), formerly known as “Condition E” and also known as I2. Record the results in units of grams eluted per 10 minutes (g/10 min). The melt index is inversely proportional to the weight average molecular weight of the polyethylene, although the inverse proportionality is not linear. Thus, the higher the molecular weight, the lower the melting index.

[0055] Movable array rheometer (MDR) test method. Run the MDR test method at 182 °C per ASTM D5289-12, Standard Test Method for Vulcanization of Rubber Property Using Rotorless Cure Meters, version of the method using sealed twist shear cure meters in an instrument Alpha Technologies MDR 2000 using bead samples from the Bead Preparation Method.

[0056] Peroxide Cure Test Method. The extent of cure is characterized as maximum torque (MH) measured at 182 °C in inch-pounds (lb.-in.) using the MDR test method and soaked granules of peroxide-curable polyolefin composition prepared according to Method of Granule Preparation. 1.00 lb.-in. = 0.113 Newton-meter (Nm). The higher the MH value, advantageously, the greater the extent of healing.

[0057] Peroxide stability test method. Peroxide stability in the peroxide curable polyolefin composition is characterized by heating soaked granules by the Granule Preparation method, (a) in an oven at 70°C and periodically measuring the degree of curing in accordance with the Peroxide Test Method. Peroxide cure. Inch-pounds (lb-in) measurements can be taken at time 0 (initial, before heating), after 21 days at 70 °C, and after 28 days at 70 °C. The smaller the loss of cure value over time, for 28 days at 70°C, the greater the stability of the peroxide in the peroxide curable polyolefin composition. In some aspects, the peroxide curable polyolefin composition and the peroxide cured polyolefin product prepared therefrom are characterized by peroxide stability measured according to the Peroxide Stability Test Method after 28 days at 70°C of 2 .00 to 3.00 Ib.-in. alternatively, the peroxide stability measured according to the peroxide stability test method after 28 days at 70°C greater than 90% (e.g. 91% to 99%) of the time 0 value.

[0058] Burn Time Test Method. This method characterizes the burn resistance as the time ts1, to increase 0.113 NM (1 pound-inch) above the minimum torque (ML) measured at 140 °C using the MDR test method and soaked granules of the peroxide curable polyolefin composition prepared according to the Granule Preparation Method. 1.00 lb.-in. = 0.113 Newton-meter (Nm). The longer the ts1 time, the advantageously greater the extent of abrasion resistance (also known as burn delay). In some aspects, the peroxide curable polyolefin composition and the peroxide cured polyolefin product prepared therefrom are characterized by resistance to cooling (MDR ts1) measured according to the Burn Time Test Method from 30 to 95 minutes.

[0059] If desired, a graph of ts1 at 140 °C in minutes (y axis) versus maximum torque (MH) at 182 °C in Ib.-in. (x axis) can be drawn. For inventive compositions that have different concentrations of BOTAP, but have the same concentration of organic peroxide (B) and any coagent (D) or optional additives, the graph can be fitted to a first line with a negative slope with compositions with higher concentrations of BOTAP with higher ts1 values and compositions with lower concentrations of BOTAP having lower ts1 values. For other inventive compositions that have the same different concentrations of BOTAP and the same concentrations of any coagent (D) or optional additives, but a different concentration of organic peroxide (B) than used to plot the first line, a second plot of ts1 at 140 °C in minutes (y-axis) as a function of maximum torque (MH) at 182 °C in Ib.-in. (x axis) can be drawn. The second plot can be fitted to a second line that has a negative slope with compositions with higher BOTAP concentrations having higher ts1 values and compositions with lower BOTAP concentrations having lower ts1 values. If plotted on the same graph, the first and second lines can have different slopes and can be separated from each other. Such graphics for the inventive examples are available upon request.

[0060] Sweat test method. Add 50 g of bead samples into a covered glass vial and the resulting vials containing the sample in an oven at 50 °C for 21 days. Remove the vials containing aged samples from the oven and allow the aged samples to equilibrate to room temperature. For aged samples, add 80 mL of acetonitrile and gently stir the resulting mixture with a stir stick for 70 seconds. Allow the resulting mixture to stand for 56 days at room temperature. After 56 days, quantify the amount of additives in the acetonitrile portion of the mixture using high performance liquid chromatography-ultraviolet light detector (HPLC-UV). Record the results in parts per million (ppm). (DSTDP cannot be analyzed for sweat using this method.) The lower the ppm value, the less the amount of sweat. In some aspects, the peroxide-curable polyolefin composition and the peroxide-curable polyolefin product prepared therefrom are characterized by BOTAP sweating measured according to the Sweat Test Method from 0.0 to 2 ppm, alternatively > 0 to 1 ppm. In some aspects, the peroxide curable polyolefin composition contains constituent (B) which is dicumyl peroxide (DiCup) and the peroxide cured polyolefin product prepared therefrom is characterized by a DiCup sweat, measured according to the method of sweat test, from 60 to 90 ppm.

[0061] In some aspects, the peroxide-curable polyolefin composition and the peroxide-cured polyolefin product prepared therefrom are characterized by a combination of at least two of characterizations (i) to (v): (i) a dissipation factor measured according to the Dissipation Factor Test Method from 0.028% to 0.099%; (ii) a peroxide stability measured according to the Peroxide Stability Test Method after 28 days at 70 °C of 2.00 to 3.00 Ib.-in, alternatively, the peroxide stability measured according to the Peroxide stability test method after 28 days at 70 °C greater than 90% (eg 91% to 99%) of the time value 0; (iii) BOTAP sweating measured according to the Sweat Test Method from 0.0 to 2 ppm, alternatively > 0 to 1 ppm; (iv) DiCup sweating measured according to the Sweat Test Method from 60 to 90 ppm; (v) Burn resistance (MDR ts1) measured according to the 30 to 95 Minute Burn Time Test Method. In some respects, the combination is: (i) and (ii); alternatively (ii) and (iv); alternatively (ii) and (v); alternatively (i), (ii) and (v); alternatively (i), (ii), (iv) and (v); alternatively, each of (i) to (v).

EXAMPLES

[0062] Constituent (A1): a pcLDPE characterized by a melting index (190°C, 2.16 kg), “I2”, of 2.1 g/10 min and a density of 0.92 g/cm3 ( “PE1”).

[0063] Constituent (B1): dicumyl peroxide (“DiCup”).

[0064] Constituent (C1): BNX-565 (4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-bis(1,1- dimethylethyl) - phenol, “BOTAP”).

[0065] Constituent (D1): alpha-methylstyrene dimer (“AMSD”).

[0066] Constituent (E1): CYANOX 1790 (tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4,6-trione).

[0067] Constituent (E2): distearyl thiodipropionate (“DSTDP”).

[0068] Constituent (E3): NAUGARD 445 (bis(4-(1-methyl-1-phenylethyl)phenyl) amine).

[0069] Constituent (E4): LOWINOX TBP-6 (2,2'-thiobis(6-t-butyl-4-methylphenol).

[0070] Constituent (E5): LOWINOX TBM-6 (2,2'-thiobis(2-t-butyl-5-methylphenol).

[0071] Constituent (F1): LOWILITE 62 (butanedioic acid dimethyl ester, polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine-ethanol).

[0072] The Granule Preparation Method and teachings herein prepared Comparative Examples 1 to 3 (CE1 to CE3) and Inventive Examples 1 to 8 (IE1 to IE8) by mixing the peroxide curable polyolefin resin (A1) with the first antioxidant (C1) and any second antioxidant(s) (E1) to (E4) and any HALS (F1) to give bulk blends, which were then granulated separately to give Comparative Preparations CP1 to CP3 and Preparations inventive IP1 to IP8. The parts by weight of Comparative Preparations CP1 to CP3 and Inventive Preparations IP1 to IP8 were separately soaked with parts by weight of the organic peroxide (B1) and any co-agent (D1), to give Comparative Examples CE1 to CE3 and Inventive Examples IE1 to IE8, respectively. The compositions of CE1 to CE3 and IE1 to IE8 are described later in Tables 1, 2 and 3, respectively.

[0073] Comparative Examples CE1 to CE3 and Inventive Examples IE1 to IE8 were tested for peroxide stability according to Peroxide Stability Test Method, burn resistance according to Burn Time Test Method and with respect to the dissipation factor in accordance with the Dissipation and Dielectric Constant Test Methods as described above. The results are recorded below in Tables 1 and 2. Tested for sweat additives according to the Sweat Test Method; results are recorded further in Table 3. Table 1: Compositions and test results for comparative examples. ("0" means 0.00)

[0074] In Table 1, the peroxide-curable polyolefin composition and the peroxide-cured polyolefin product of Comparative Example 1 contained, among other things, a problematic combination of three antioxidants, CYANOX 1790, DSTDP and NAUGARD 445 and showed substantial instability of peroxide. The peroxide curable polyolefin composition and peroxide cured polyolefin product of Comparative Example 2 contained, among other things, a problematic combination of antioxidant LOWINOX TBP-6 and HALS LOWILITE 62 and showed some peroxide instability. The peroxide curable polyolefin composition and the peroxide cured polyolefin product of Comparative Example 3 contained, among other things, a problematic combination of two antioxidants, CYANOX 1790 and DSTDP, and showed extreme peroxide instability. Table 2: Compositions and test results for the inventive examples. ("0" means 0.00)

[0075] As shown in Table 2, the peroxide curable polyolefin composition and the peroxide cured polyolefin product of Inventive Examples 1 to 6 (IE1 to IE6) contained, among other things, the unique antioxidant BNX-565 (4- [[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-bis(1,1-dimethylethyl)-phenol, "BOTAP") and showed robust stability of peroxide. The peroxide curable polyolefin composition and peroxide cured polyolefin product of inventive Examples 7 and 8 (IE7 and IE8) contained, among other things, the first antioxidant BNX-565 (4-[[4,6-bis(octylthio )-1,3,5-triazin-2-yl]amino]-2,6-bis(1,1-dimethylethyl)-phenol, "BOTAP") and a second antioxidant which was CYANOX 1790 (IE7) or LOWINOX TBM -6 (IE8) and showed robust peroxide stability. Furthermore, all inventive compositions and products showed an excellent dissipation factor. Thus, the inventive peroxide-curable polyolefin composition and the peroxide-cured polyolefin product have robust peroxide stability relative to a comparative composition utilizing (a) a combination of antioxidants CYANOX 1790 and DSTDP and NAUGARD 445 or (b) a combination of antioxidants CYANOX 1790 and DSTDP, or (c) a combination of antioxidant LOWINOX TBP-6 and the HALS LOWILITE 62. The peroxide curable polyolefin composition of the invention and the peroxide cured polyolefin product have a superior dissipation factor relative to to a comparative composition using (a) a combination of antioxidants CYANOX 1790 and DSTDP and NAUGARD 445. The abrasion resistance (MDR ts1) of the peroxide curable polyolefin composition and the peroxide cured polyolefin product can be plotted (available upon request) with ts1 at 140 °C in minutes on the y-axis and maximum torque (MH) at 182 °C in lb.-in on the x-axis. The abrasion resistance (MDR ts1) of the peroxide curable polyolefin composition and the peroxide cured polyolefin product is excellent. The foregoing data show that the composition and product of the invention have performance characteristics that make the composition and product of the invention useful in a variety of applications, including as a component of a coated conductor coating, such as a coated wire or a coated cable. Table 3: Sweat test results for the inventive examples. (N/A means not applicable)

[0076] As shown by the sweating data for different additives above in Table 3, a comparative composition with CYANOX 1790 and NAUGARD 445 (CE1) produced sweating of 50 ppm and 9 ppm, respectively. Compositions with BOTAP have surprisingly less sweating than these additives. For IE1 with 0.12 wt% BOTAP, sweating outside BOTAP was not detected. For compositions with 0.24% by weight of BOTAP (IE2, IE7 and IE8), 0.36% by weight of BOTAP (IE3) or 0.42% by weight of BOTAP (IE4), BOTAP sweating was less than 1 ppm (<1 ppm), very low beneficial level. Furthermore, the inventive compositions IE1 to IE4, IE7 and IE8 each had less DiCup sweating (B1) than the comparative composition CE1.

[0077] Incorporate the following claims by reference here as numbered aspects, except replace “claim” and “claims” with “aspect” or “aspects”, respectively.

Claims (11)

1. Peroxide-curable polyolefin composition, characterized in that it comprises the constituents (A) to (C): (A) a peroxide-curable polyolefin resin, (B) an organic peroxide, and (C) 4-[[ 4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-bis(1,1-dimethylethyl)-phenol ("BOTAP"); wherein the peroxide-curable polyolefin composition contains from 95.0 to 99.70 percent by weight (% by weight) of (A), from 0.20 to 2.5% by weight of (B) and 0 .01 to 0.50% by weight of (C), and further comprising (i) at least (D) one coagent (H2C=C(H)(CH2)b-functional) (D) which is an alpha-dimer -methylstyrene, or (ii) at least (E) a second antioxidant which is (tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2, 4,6-trione, all based on the total weight % of the peroxide curable polyolefin composition. 2. Peroxide-curable polyolefin composition according to claim 1, characterized in that the peroxide-curable polyolefin resin (A) is (i) a peroxide-curable polyethylene resin (“pcPE”); or (ii) a pcPE which is a peroxide curable low density polyethylene resin ("pcLDPE"); or (iii) a pcPE which is a peroxide curable high density polyethylene resin ("pcHDPE"); or (iv) a pcPE which is a blend of an ethylene (C1-C4) alkyl acrylate (EAA) copolymer and a peroxide curable polyethylene ("pcPE"); or (v) a pcPE which is a pcLDPE; and set a melt index (190 °C, 2.16 kg), “I2”, from 0.5 to 3.0 grams per 10 minutes (g/10 min) and a density from 0.90 to 0.95 grams per cubic centimeter (g/cm3); or (vi) a combination of any two or more of (i) through (iv). 3. Peroxide-curable polyolefin composition according to any one of claims 1 or 2, characterized in that the organic peroxide (B) is dicumyl peroxide. 4. Peroxide-curable polyolefin composition, according to any one of claims 1 to 3, characterized in that (i) the organic peroxide (B) has from 0.20 to 2.10% by weight; or (ii) the organic peroxide (B) having from 0.50 to 2.00% by weight; or (iii) BOTAP (C) ester from 0.015 to 0.50% by weight; or (iv) BOTAP (C) is from 0.05 to 0.42% by weight; or (v) or a combination of (i) and (iii), (i) and (iv), (ii) and (iii), or (ii) and (iv); wherein all % by weight is based on the total weight of the peroxide curable polyolefin composition. 5. Peroxide-curable polyolefin composition according to any one of claims 1 to 4, characterized in that it further comprises (i) at least one coagent (H2C=C(H)(CH2)b-functional) (D.a) , where the subscript b is an integer from 0 to 2; or (ii) at least one second antioxidant (E.a); or (iii) (F.a) a hindered amine light stabilizer ("HALS"); or (iv) (G.a) a flame retardant; or (v) (H.a) a water tree retardant or electrical tree tree retardant (H); or (vi) (I.a.) a dye; or (vii) (J.a.) a methyl radical scavenger; or (viii) (K.a) a liquid aromatic or saturated hydrocarbon; or (ix) a combination of (i) and (ii); or (x) a combination of (i), (ii) and at least one of (iii) through (viii); or (xi) a combination of (i), (ii), (iii) and optionally 0 to 2 of (iv) to (viii); all of which being the combined weight of (D.a), (E.a), (F.a), (G.a), (H.a), (I.a), (J.a), and (K.a) > 0 to 4.69% by weight of total weight of the peroxide curable polyolefin composition. 6. Peroxide-curable polyolefin composition, according to claim 5, characterized in that: (i) (D.a) the at least one coagent (H2C=C(H)(CH2)b-functional) is (D.b) alpha-methylstyrene dimer or a multi-(H2C=C(H)(CH2)b-functional) coagent having two or three groups (H2C=C(H)(CH2)b-, where the subscript b is as defined above or below, or (ii) the at least one (E.a) second antioxidant (E.b) is absent, tris [(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5- triazine-2,4,6-trione or 4,4'-thiobis(2-t-butyl-5-methylphenol; or (iii) the (F.a) HALS be (F.b): butanedioic acid dimethyl ester, polymer with 4 -hydroxy-2,2,6,6-tetramethyl-1-piperidine-ethanol; or (iv) the flame retardant (G.a) is a metal hydroxide, a swelling compound or a halogenated compound, or (v) the flame retardant water tree-retardant or electrical tree-retardant (H.a) which is (H.b) a silane or a polyethylene glycol; or (vi) the dye (I.a) is carbon black (I.b), or (vii) the (J.a) tar remover methyl radical is (J.b) a 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl derivative; or (viii) the (K.a) LASH is (K.b) an alkyl-substituted alkane or arene; or (ix) a combination of (i) and (ii); or (x) a combination of (i), (ii) and at least one of (iii) through (viii); or (xi) a combination of (i), (ii), (iii) and optionally 0 to 2 of (iv) to (viii); and wherein each of the constituents (D.b), (F.b), (G.b), (H.b), (I.b), (J.b) and (K.b) is independently (a) from 0.30 to 2.10% by weight ; or (b) from 0.05 to 0.5% by weight; or (c) from 0.010 to 0.35% by weight; and each (E.b) second antioxidant being independently (a) from 0.01 to 0.2% by weight; or (b) from 0.01 to 0.10% by weight; wherein all the weight % based on the total weight of the peroxide curable polyolefin composition and the combined weight of (D.b), (E.b), (F.b), (G.b), (H.b), (I.b), (J.b) ), and (K.b) is > 0.01 to 4.69% by weight of the total weight of the peroxide-curable polyolefin composition. 7. A method of preparing a peroxide-curable polyolefin composition, characterized in that the method comprises contacting effective amounts of constituents (A) to (C) with: (A) a peroxide-curable polyolefin resin, (B) a peroxide organic (B), and (C) 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-bis(1,1-dimethylethyl)- phenol; to give the peroxide-curable composition, the peroxide-curable polyolefin composition containing from 95.0 to 99.70 weight percent (wt%) of (A), from 0.20 to 2.5% by weight of (B) and from 0.01 to 0.50% by weight of (C), and further comprising (i) at least one (D) co-agent (H2C=C(H)(CH2)b-functional) (D) which is an alpha-methylstyrene dimer, or (ii) at least (E) a second antioxidant which is (tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1 ,3,5-triazine-2,4,6-trione, all based on the total weight % of the peroxide curable polyolefin composition. 8. Peroxide-cured polyolefin product, which is a reaction product of the cure of the peroxide-curable polyolefin composition, as defined in any one of claims 1 to 6, characterized in that it results in the peroxide-cured polyolefin product. 9. Manufactured article, characterized in that it comprises a molded form of the peroxide-cured polyolefin product as defined in claim 8. 10. Coated conductor, comprising a conductive core and an insulating layer at least partially covering the conductive core, characterized in that at least a portion of the insulating layer comprises the peroxide-curable polyolefin composition as defined in any one of claims 1 to 6, or the peroxide cured polyolefin product as defined in claim 8. 11. Method of conducting electricity, characterized in that the method comprises applying a voltage across the conductive core of the coated conductor as defined in claim 10, in order to generate a flow of electricity through the conductive core.